Production of arylides of 2.3-hydroxynaphthoic acid



Patented July 11, 1933 n sraras THERESA SUSEMII-IL KERR, OF'BUFFALO, ASSIGNOR'TO NATIONAL ANILINE w AND CHEMICAL COMPANY, NEW YORK, N. K, A CORPORATIGN'OF NEW YORK.

PRODUCTION or ARYLIDES or as-nynn oxy mrnrnoic ACID No Drawing. Application filed July 14,

My invention relates to the production of arylides of 2.3-hydroxynaphthoic acid, and particularly to improved methods of producing the same whereby a high yield is'oL- tained and a product of high purity is produced.

The arylides of 2.3hydroxynaphthoic acid are employed as intermediate products in the production of certain classes of dyes and are also used in the production of-other intermediates. Heretofore the arylides have been produced by treating a mixture containing 2.S-hydroxynaphthoic acid and an arylamine with a halide such as phosphorous tric-hloride or thionyl chloride. he amount of the phosphorous trichloride or other halide used in carrying out the reaction has heretofore been in large excess. e. g from 30 to .150 per cent excess, of the theoretical amount required to produce the halide of the acid.

I have discovered that by first'treating the '2.3-hydroxynaphthoic acid with a material capable of reacting with said acid to produce an acid'halide and subsequently reacting the resultant mixture, which presumably contains 2.3-hydroxynaphthoyl halide, with an arylamine, the yield and purity of the product obtained are materially improved over that obtained by processes heretofore employed. Further, I have discovered that the use of a large excess of the halide over the theoretical amount required to produce 2.3- hydroxynaphthoyl chloride tends to reduce the yield and the quality of theresulting arylide of the QB-hydroxynaphthoic acid. produced; I l

Among the objects of my invention are to provide an improved process for producing the arylides of 2.3-hydroxynaphthoic acid, to

increase the yield of the product obtained by the reaction over thatheretofore obtainable, to produce an arylide of '2.3-hydroxynaphthoic acid of high'purity, and to reduce the amount of acid halide forming material employed in carrying out the process. These and other objects and features of my invention will appear from the following description thereof. s V a In accordance with my invention I first treat 2.3-hydroxyiiaphthoic acid, preferably 1931. Serial No. 550,811

in the presence of an indiflierent solvent or diluent liquid, Witha halide capable of reacting' with the acid to producethe corresponding acid halide. Thereafter. I react the resulting mixture with an arylamine. The solimmiscible with Water and whlch have a boiling point of 110 C. or above, more particularly about 130 C. or higher/ 7 The halides employed in carrying out the 7 process maybe phosphorus trichlorid'e, phos phorous oxychloride, thionylv chloride orother chlorides or halides which upon interaction" with 2.3-hydroxynaphthoic acid are capable of yielding the corresponding acid halides. .The' arylamine used in nrnducin I the arylides; of 2.3-hydroxynaphthoic acid will depend in each case upon the product desired. qI may, for instance, employ a primary or secondary aromatic am1ne,such as the primary and secondary aminesfof the I,

benzene, diphenyl, and naphthalene, etc. series, including their l alkyl-, chloronitro-,

hydroxyr, alkoXy-, carbo y-, and amino-derivatives (as for example, aniline, o-toluidine, alphaorbeta-naphthylamine, tetrahydroalpha-naphthylamine, N-ethylaniline, 2.5-

. and othermonoanddi-chloranilines,chloroaoc toluidines, o' a-minophenol, 1.3- or 1.4:- or 1.5-

or 1.6- or 1.7 or 2.6- 01' 2.7- aminonaphthol,

anisidines, cresidine, 4-chloro-o-anisidine, aminonaphthol eth'ers, monoor para-am nobenzolc 301d, cresotmic acid, para-ammosalicylic acid, 2.4c-tolylenediamine, phenylen'ediamine, etci). 3 v I I In carrying out the process in'accordance: with my invention,I employ substantially the theoretical amount of halide required for reaction withfthe acid to produce the acid benzidine, tolidine, dianisidine,

tion, but I 'have'found that the presence of a halide. I may employ from 1 to 10% in ex;

cess of that theoretically required for the reaclarge excessof the halide in the reaction mixture tends to reduce the yield and decrease the quality of the resulting product. I therefore intend that the expression substantially the theoretical amount of a halide as hereinafter employed in the specification and claims shall include asmall excess of the halide, such as 1 to Iprefer to use about the theoretical amount of the arylamine required for the reaction although 1 may in seine instances employ an excess of tliearylainine. a

In order that my invention \villbe more clca 'ly undcrstoo jhe following example is given'by Way of illustration of the preferred method of carrying out my invention. However, my invention is not limited to the specific exam ile cited and therefore do not intend thatmy invention should be restricted to the particular method recited therein.

,Em/zm-plc f'lo a: Well-stirred mixture of 60 parts by \veigl'it of2.3hydroxynaphthoic acid and 510 parts of meno-chlorbenzene there is slowly added parts of phosphorus trichloride; the mixture is stirred at room tempera-ture for about 10 to 15 hours and thereafter parts of o-to-luidine are-gradually introduced into the Well-stirred mixture. Themixture is heated to 110? nnder a reflux condenseruntil the evolution of hydrogen chloride has greatly diminished, andthen the mixture is heated to boiling, i. e-., refluxing temperature which is about 132- C, until practically no more hydrogen chloride is evolved. The resulting solution of the arylride then added to an: iced aqueous solution of sodium carbonate containing an amount of sodium. carbonate in Sl1llhQXOGSS of that requiredto effect the neutralization of any acid which maybe present. The o-teluidide 1of pr c s obtained. when a mixture of the acid and 2}3-hydroxynaphthoic acid is thus obtained in the form of an insoluble precipitate, which I is filtered off and washed with Warm Water.-

, lVliile I have described a process-inwhich the arylide is precipitated by addition of the reaction mixture to an iced solutioirof so-v dium carbonate (soda ash), it may bedesir ablei i some instances to effect theprecipitationiof the aryl'ide directly from the diluent in a non-aqueous"mixture by the use of-a diluent material ll'LWlllCll the arylidejis insoluble; YVlien adiluent of this type employed thc resultingarylide is obtained directly fil tration. .For example, when producing the arylides of anilinei or lfleillliflllll'llHG and 2.3-

l iydroxynaphthoic acidfl may employ chlor: a

benzene as the diluentfor the acid. The aryl-- ide-produced is insoliiblein cliloi'benzene and i therefore may be obtained by filtration:

ithout addition of the reaction mixture to 7 an aqueous solut-ion.' L a The yield and quality of the arylide of 2.3-

hydi'oxynaphthoic acid thus obtained by the i above described is superior to that the arylamine treated t'ivithf phosphorous trichloride o'r othe'r halide capable of yielding acid halides as in the method previously employed. It will also be noted in carrying out my process that the amount of phosphorous trichloride or other halide employed only about to of that heretofore employed when the acid and amine were mixed prior to treatment With the halide. The increase in yield and purity of the product obtained andithe decrease in the amount by the foregoing example illustrative of the fined by the claims. I

I claim: 7 1. A process for making preferred form of myinyention exceptas clean arylide of'2.3-

hydroxynaphthoic acid Whichcompriseslirst reacting 2.i -hydroxynaphthoic acid with a halide capable of reacting with said acid to produce an acid halide, andsubsequently reacting the resulting mixture'with an .arylannne.

2. Aprocess for making an arylide of 2.3-

hydroxynaphth oic acid which coinprisesfirst treating 2.3-hyd'roxynaphthoic acid, with substantially the theoreticalamount of a halide capable of reacting \vi-th'said acid to produce an acid halide, and subsequently reacting the resulting mixture with an a-rylam ne.

A process for making'an,arylide of 2.3-

hydroXyna-phthoic acid Which comprises first acting 2.S-hydroxynaphthoic acidin an inlie;

different diluent hich is immiscible with 7 Water. 7 with substantially amountof a halide capable of reacting with said acid to produce an-acid ha ide, and sub sequently reacting the resultingmixture with an arylamine. I a

l. Aiproeessfor making an arylide of 2.3- hydroxynaphthoic acid which comprises-first treating 2.3-hydroxynaphthoic acid with substantially'the theoretical-amount of a halide he theoretical I;

capable of reacting with said acid to pro- 7 duce "an acid halide, and subsequently reacting the resulting'mixture with substantially'the theoretical amonnt'of an arylamine. ,5.. A process for making an arylide of2.3-

hydroxynaphthoic acid which comprises first treating 2.3 -hydroxynaphthoic acid With substantiallythe theoretical amount of phosphoroustrichloride in'th'e presence of an indiffereii-tdiluent, and subsequently reacting theresultin mixture withan' arylamine. 6. A process for makingan arylide'of 2.?

ISO

hydroxynaphthoic acid which comprises first reacting 2.3 hydroxynaphthoic acid with phosphorous trichloride, and subsequently reacting theresulting mixture with an arylamine.

7. A process for making the o-toluidide of 2.3-hydroxynaphthoic acid which coinprises first reacting 2.3-hydroxynaphthoic acid with substantially the theoretical amount of'phosphorous trichloride in the presence of an indifferent diluent, and subsequently reacting the resulting mixture with o-toluidine. v

8. A process for making an arylide of 2.3- hydroxynaphthoic acid which comprises first reacting 2.S-hydroxynaphthoic acid with substantially the theoretical amount of a halide capable of reacting with said acid to produce an acid halide subsequently adding an arylamine to the resulting mix ture and heating the same. a

9. A process for making an arylide of 2.3-hydroxynaphthoic acid which comprises first reacting 2.3-hydroxynaphthoic acid in the presence of an'indillerent diluent in which the arylide to be produced is insoluble with substantially the theoretical amount of a halide capable of reacting with said acid to produce an acid halide, subsequently reacting the resulting mixture with an arylamine selected from the amines of the benzene and naphthalene series, and separating the arylide of 2.S-hydroxynaphthoic acid thus produced from said indifferent diluent.

10. A process of making the otoluidide of 2.3-hydroxynaphthoic acid which comprises slowly adding substantially the theoretical'amount of phosphorous trichloride to 2.B-hydroxynaphthoic acid and chlorbenzene, to produce the acid chloride, stirring the mixture at room ten1perature,subsequently gradually adding to the reaction mixture substantially the theoretical amount of o-toluidine required to form the o-toluidide of the acid, heating the mixture at about C. with refluxing until the evolution of-hydrogen chloride has diminished, then heating the mixture to boiling until no more hydrogen chloride is evolved adding the resulting mixture to an iced aqueous solution of sodium carbonate in WlllCll the sodi- Lnn carbonate is present in excess of that required to effect neutralization of any acld that may be present in the mixture, whereby the o-toluidide of 2.3-hydroxynaphthoic acid is precipitated,filtering off the precipitate,

V and washing the precipitate with warm waing mixture with an arylainine selected from,

the amines of the benzene and naphthalene series.

12. A process for making an arylide of 2.3-

hydroxynaphthoic acid which comprises first reacting 2.3-hydroxynaphthoic acid with substantially the theoretical amount of a halide selected from the group consisting of phosphorous trichloride, phosphorous oxychloride and thionyl chloride, and subsequently reacting the resulting mixture Wite an arylamine.

13. A process for making an arylide of 2.3-hydroxynaphthoic acid which comprises first reacting 2.3-hydroxynaphthoic acid in the presence of an indifferent diluent with F substantially the theoretical amount of a halide selected from the group consisting of phosphorous trichloride, phosphorous oxychloride and thionyl chloride, and subse quently reacting the resulting mixture with M an-arylamine selected from the amines of the benzene and naphthalene series.

In witness whereof, I have hereunto set my hand.

THERESA SUSEMIHL KERR.

CERTKFIGATE OF CORRECTION.

Patent No. 1,917,890. July 11, 1933.

THERESA SUSEMIHL KERR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring currectisn as fotiows: Page 2, line 108, claim 3, for "acting" read "reacting"; and that the said Letters Patent should be read with this correctien therein that the same may nonfat-m to the record of the case in the Patent Office.

Signed and sealed this 22nd. day of August, A. D. 1933.

M. L Meorez (Seal) Acting Commissioner of Patents. 

